Vat dyestuffs of the anthraquinone series



Patented July 5, 1938 UNITED STATES PATENT OFFICE VAT DYESTUFFS OF THEANTHRAQUINONE SERIES No Drawing. Application August 23, 1935, Serial No.37,601. In Germany August 29, 1934 3 Claims.

The present invention relates to new anthraquinone derivatives.

I have found that new and valuable anthraquinone derivatives areobtained by causing halogen alkyl sulfonic acids to react upon mercaptoanthraquinones. The new compounds which are obtainable thereby and whichare the object of my present invention may be defined asanthraquinonyl-alkyl-thioethers, wherein the alkyl residues bearsulfonic acid groups. These anthraquinone derivatives are water solubleproducts and can be used for directly dyeing animal fibers or asintermediates for the preparation of dyestuffs. The new dyestuffs show ayellow to black coloration and represent in form of the alkali metalsalts well crystallized compounds, which dissolve in water either withyellow, violet or blue to gray coloration and dye wool from an acid baththe same shades. The dyestuffs show good equalizing properties.Obviously, the anthraquinone nucleus may contain various substituentswithout departing from the sense of my invention. Of particularimportance are such compounds as contain besides the sulfur containinggroup in one B-position. halogen atoms in the other p-position of thesame nucleus and amino groups in 1- or ll-position. of the same nucleus,examples for such starting materials are, for instance,1amino-2-mercapto-4-aminoanthraquinones, the 4-amino group of whichcontains substituents like the benzene, toluene, hexahydrobenzene orother aromatic or hydroaromatic residues. Furthermore, my inventionisnot restricted to the presence of only one sulfur containing group ofthe character described, derivatives of polymercaptoanthraquinones, suchas of a 2.3-dimercaptoanthraquinone being included within the scope ofmy claims. Examples of other suitable starting materials are, forinstance, 1- mercaptoanthraquinone, I-amino-Z-mercaptoanthraquinone,1.4-diamino-2-chloro-3-mercaptoanthraquinone,4.4'-diamino-3.3-dimercapto- 1.1-dianthraquinonylamines,l-amino-2-mercapto-4-arylidoanthraquinone-fi-sulfonic acids, 1-amino-Z-mercaptoanthraquinone-4-arylido sulfonic acids (i. e. compoundswhich contain a sulfonic acid group in the aryl residue which isattached to the nitrogen), furthermore, l-amino- 2-mercapto-6- or'I-chloroanthraquinones and the like. Suitable halogen alkyl sulfonicacids are, for instance, chloroethane sulfonic acid, chloropropanesulfonic acid, hydroxychloropropane sulfonic acid andp-chlorodiethylether-,8'- sulfonic acid, it being understood thatderivatives of lower alkyl groups are preferably employed for myinvention.

The reaction is performed in an aqueous solution or in dilute alcoholicsolution at a temperature of about 50 to about C. In case the mercaptanein question which serves as starting material has not been applied inform of an inorganic salt from the very beginning, caustic alkalies,alkali carbonate and the like may be added as acid binding agents. Thewater soluble thioethers may be isolated in the usual manner, forinstance, by salting out.

The following examples will illustrate the invention, without, however,restricting it thereto, the parts being by weight:-

Example 1 30 parts of l-mercaptoanthraquinone are dissolved whileheating in 800 parts of an aqueous alcohol of 50% strength with theaddition of 40 parts of a 30% aqueous sodium lye. Into the clear,reddish-violet mercaptane solution, 50 parts of the sodium salt ofchloroethane sulfonic acid are introduced and the mixture is heated toboiling, until the reddish-violet coloration of the solution has turnedto brown.

' The working up is performed by acidifying the reaction mass, thedisulfide formed as by-product and the starting material are filtered01f and from the filtrate the sulfonic acid formed is isolated bysalting out in form of its potassium salt by means of potassiumchloride. Similar results are obtained by replacing the chloroethanesulfonic acid by the corresponding amount of thep-chlorodiethylether-fl'sulfonic acid.

Example 2 7.2 parts of l -amino-2-mercapto-4-para-toluidoanthraquinon(obtainable from l-amino-Z- bromo-4-para-toluidoanthraquinone by atreatment with sodium sulfide) are dissolved in 60 parts of ethanol,parts of Water and with the addition of 6 parts of a 30% caustic sodasolution, whereupon the disulfide, which might be present, is filteredoff. The bluish-violet solution is heated toboiling for some hours whilerefluxing after the addition of 12 parts of chloroethane sulfonic acid(sodium salt). Most part of the reaction product crystallizes whileheating, and may be directly sucked off when the reaction is finished.The bluish-green dyestuff being difficultly soluble in water may beobtained by recrystallization from aqueous methanol in an absolutelypure state. It dyes wool from an acid bath greenish blue shades ofexcellent fastness properties.

acid, an analogous dyestuff is obtained which corresponds to thefollowing formula:

SCHzGH2SOaNa I H2 H2 0 EN oo 7 H2 H2 7 It dyes more reddish and clearershades than the dyestuff mentioned above.

Example 3 30 parts of the sodium saltof lA-d'iamino-Z-chloro-3-mercaptoanthraquinone, which may be obtained by a reaction ofmolecular. amounts of sodium sulfide and 1,4-diamino-2,3 dich1oroanthraquinone, are heated to boiling while stirring with 500 parts ofaqueous ethanol of 50% strength and 40 parts of the sodium salt ofchloroethane sulfonic acid, until the presence of mercapto groups can nolonger be observed. After cooling the separated dyestuff is sucked off.For purification the starting material is once more redissolved fromwater and salted out by the addition of common salt in form ofits bluishviolet sodium salt.

Wool is dyed clear bluish-violet shades of good equalizing propertiesand good fastness to light.

A more bluish dyestuff is obtained by causing sulfite to react upon thecompound obtained the chlorine being replaced by the sulfonic acidgroup.

Example 4 15 parts of the sodium salt of 1,4-diamino-2,3'-dimercaptoanthraquinone (obtainable from L4-diamino-2,3-dichloroanthraquinone by the action of an excess of sodiumsulfide) are heated for some hours to boiling while refluxing with 30parts of the sodium salt of chloroethane sulfonic acid and 3 parts ofsodium bicarbonate in 300 parts of aqueous ethanol. The reaction productis sucked 01? after cooling. The dyestuif may be recrystallized frompyridine water. In a dry state it represents a blue crystalline powderand dyes wool from an acid bath blue shades.

Example 5 When brominating the 4,4'-diamino-1,1'-dianthrimide innitrobenzene, two bromine atoms are absorbed; by melting this productwith sodium sulfide a dimercaptane is obtained which is L'The compoundsof the following formula o ism /S-C2H.4-S( )3H I wherein X represents amember of the, group consisting of hydrogen, aryl and hydroaryl, and

wherein Y represents a member of the group consisting of hydrogen andchlorine.

2. The product of the following formula:

H; I n

3. The product of the following formula: I o NHi i FRITZ BAUMANN.

